1(4&#39;-methylpentyl)-4-substituted ethylcyclohexane derivatives, organoleptic uses thereof, process for producing same, and process intermediates therefor

ABSTRACT

Described are 1(4&#39;-methylpentyl)-4-substituted ethylcyclohexane derivatives defined according to the structure: ##STR1## wherein R 3 , R 4 , R 5  and R 6  are the same or different hydrogen or methyl; wherein the dashed line represents a carbon carbon single bond or a carbon carbon double bond; wherein the wavy line represents a carbon carbon single bond or a carbon carbon double bond; with the proviso that when the wavy line is a carbon carbon single bond then the dashed line is a carbon carbon single bond; wherein Y represents a moiety selected from the group consisting of: ##STR2## wherein H represents hydrogen, C 1  -C 4  lower alkyl or C 1  -C 2  acyl; and wherein R 1  represents C 1  -C 4  lower alkyl with the additional proviso that when Y is the moiety: ##STR3## then the dashed line is a carbon carbon single bond, and uses thereof in augmenting, enhancing or imparting aromas in or to perfume compositions, perfumed articles and colognes. Also described are processes for producing the above-mentioned 1(4&#39;-methylpentyl)-4-substituted ethylcyclohexane derivatives as well as intermediates used in said processes.

BACKGROUND OF THE INVENTION

The present invention relates to 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives defined according to the structure:##STR4## wherein R₃, R₄, R₅ and R₆ are the same or different hydrogen ormethyl; wherein the dashed line represents a carbon carbon single bondor a carbon carbon double bond; wherein the wavy line represents acarbon carbon single bond or a carbon carbon double bond; with theproviso that when the wavy line is a carbon carbon single bond then thedashed line is a carbon carbon single bond; wherein Y is a moietyselected from the group consisting of: ##STR5## wherein R₂ representshydrogen, C₁ -C₄ lower alkyl or C₁ -C₂ acyl; and wherein R₁ representsC₁ -C₄ lower alkyl with the additional proviso that when Y is themoiety: ##STR6## then the dashed line is a carbon carbon single bond,and uses thereof in augmenting, enhancing or imparting aromas in or toperfume compositions, colognes and perfumed articles (including solid orliquid anionic, cationic, nonionic or zwitterionic detergents, fabricsoftener compositions, fabric softener articles, cosmetic powders, hairpreparations and perfumed polymers).

There has been considerable work performed relating to substances whichcan be used to impart (augment or enhance) fragrances (to) or (in)various consumable materials. These substances are used to diminish theuse of natural materials some of which may be in short supply and toprovide more uniform products in the finished product. In addition,there is a need to use such consumable materials in perfumes which arenon-discoloring.

Intense, substantive and long lasting patchouli, ambery, earthy, woody,peach, mimosa, camphoraceous, mahogany, piney, animalic and musky aromaswith patchouli, camphoraceous, earthy; musty, woody, green and fruitytopnotes are highly desirable for many uses in perfume compositions,perfumed articles and colognes, particularly where a patchouli note isneeded to be added to musk formulations and citrusy formulations.

Substituted ethylcyclohexane derivatives are well known for use inperfumery. Thus, British Patent No. 896,039 entitled "Method ofProducing Derivatives of the 1,1-Dimethyloctahydronaphthalene Series"discloses the generic process: ##STR7## wherein R₂, R₃ and R₄ aredisclosed to be the same or different hydrogen atoms or alkyl and R₁ isdisclosed to be hydroxy, alkyl or alkoxy, and wherein one of the dashedlines represents a carbon carbon double bond and each of the other ofthe dashed lines represent carbon carbon single bonds. British PatentNo. 896,039 discloses this process to be useful for producing products"resembling the well known class of violet perfumes". However, nothingin British Patent Specification No. 896,039 discloses or implies the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is the GC-MS spectrum for the reaction product of Example Acontaining the compound having the structure: ##STR8## (conditions: 50meter×0.32 mm methyl silicone column programmed from 75°-225° C. at 2°C. per minute).

FIG. 1B is the GC-MS spectrum for the reaction product of Example Acontaining the compound having the structure: ##STR9## (conditions: 50meter×0.32 mm CARBOWAX® 20M column programmed from 75°-225° C. at 2° C.per minute).

FIG. 2 is the NMR spectrum for the compound having the structure:##STR10## produced according to Example A.

FIG. 2A is an enlargement of section "A" of the NMR spectrum of FIG. 2.

FIG. 2B is an enlargement of section "B" of the NMR spectrum of FIG. 2.

FIG. 3 is the IR spectrum for the compound having the structure:##STR11## prepared according to Example A.

FIG. 4 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR12## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 5 is the NMR spectrum for the compound having the structure:##STR13## prepared according to Example I.

FIG. 5A is an enlargement of section "A" of the NMR spectrum of FIG. 5.

FIG. 5B is an enlargement of section "B" of the NMR spectrum of FIG. 5.

FIG. 6 is the infrared spectrum for the compound having the structure:##STR14## prepared according to Example I.

FIG. 7 is the GLC profile for the reaction product of Example IIcontaining the compound having the structure: ##STR15## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 8 is the NMR spectrum for the compound having the structure:##STR16## prepared according to Example II.

FIG. 8A is an enlargement of section "A" of the NMR spectrum of FIG. 8.

FIG. 8B is an enlargement of section "B" of the NMR spectrum of FIG. 8.

FIG. 9 is the infrared spectrum for the compound having the structure:##STR17## prepared according to Example II.

FIG. 10 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR18##

FIG. 11 is the NMR spectrum for the compound having the structure:##STR19## prepared according to Example III.

FIG. 12 is the infrared spectrum for the compound having the structure:##STR20## prepared according to Example III.

FIG. 13 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR21## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 14 is the NMR spectrum for the compound having the structure:##STR22## prepared according to Example IV.

FIG. 14A is an enlargement of section "A" of the NMR spectrum of FIG.14.

FIG. 14B is an enlargement of section "B" of the NMR spectrum of FIG.14.

FIG. 14C is an enlargement of section "C" of the NMR spectrum of FIG.14.

FIG. 15 is the infrared spectrum for the compound having the structure:##STR23## prepared according to Example IV.

FIG. 16 is the GLC profile for the reaction product of Example Vcontaining the compound having the structure: ##STR24## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 17 is the NMR spectrum for the compound having the structure:##STR25## prepared according to Example V.

FIG. 17A is an enlargement of section "A" of the NMR spectrum of FIG.17.

FIG. 17B is an enlargement of section "B" of the NMR spectrum of FIG.17.

FIG. 18 is the infrared spectrum for the compound having the structure:##STR26## prepared according to Example V.

FIG. 19 is the GLC profile for the reaction product of Example VIcontaining the compound having the structure: ##STR27## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 20 is the NMR spectrum for the mixture of compounds containing 95mole percent of the compound having the structure: ##STR28## and 5 molepercent of the compound having the structure: ##STR29## preparedaccording to Example VI.

FIG. 20A is an enlargement of section "A" of the NMR spectrum of FIG.20.

FIG. 20B is an enlargement of section "B" of the NMR spectrum of FIG.20.

FIG. 21 is the infrared spectrum for the mixture containing 95 molepercent of the compound having the structure: ##STR30## and 5 molepercent of the compound having the structure: ##STR31## preparedaccording to Example VI.

FIG. 22 is the GLC profile for the reaction product of Example VII(A)containing the compound having the structure: ##STR32##

FIG. 23 is the NMR spectrum for the compound having the structure:##STR33## prepared according to Example VII(A).

FIG. 23A is an enlargement of section "A" of the NMR spectrum of FIG.23.

FIG. 23B is an enlargement of section "B" of the NMR spectrum of FIG.23.

FIG. 24 is the infrared spectrum for the compound having the structure:##STR34## prepared according to Example VII(A).

FIG. 25 is the GLC profile for the reaction product of Example VII (B)containing the compounds having the structures: ##STR35## (conditions:CARBOWAX® 20M column programmed from 150°-220° C. at 8° C. per minute

FIG. 26 is the NMR spectrum for the mixture of compounds having thestructures: ##STR36## prepared according to Example VII(B)

FIG. 27 is the GLC profile for the reaction product of Example VII(C)containing the compounds having the structures: ##STR37##

FIG. 28 is the NMR spectrum for the mixture of compounds having thestructures: ##STR38## prepared according to Example VII(C).

FIG. 29 is the GLC profile for the reaction product of Example VIIIcontaining the compound having the structure: ##STR39## (conditions:SE-30 column programmed from 150°-220° C. at 8° C. per minute).

FIG. 30 is the NMR spectrum for the compound having the structure:##STR40## prepared according to Example VIII.

FIG. 30A is an enlargement of section "A" of the NMR spectrum of FIG.30.

FIG. 31 is the infrared spectrum for the compound having the structure:##STR41## prepared according to Example VIII.

FIG. 32 is the GLC profile for the reaction product of Example IXcontaining the compound having the structure: ##STR42##

FIG. 33 is the NMR spectrum for the compound having the structure:##STR43## prepared according to Example IX.

FIG. 34 is the infrared spectrum for the compound having the structure:##STR44## prepared according to Example IX.

FIG. 35 is the GLC profile for the reaction product of Example Xcontaining the compounds having the structures: ##STR45##

FIG. 36 is the NMR spectrum for the peak indicated by reference numeral"350" on the GLC profile of FIG. 35 for the compound having thestructure: ##STR46## prepared according to Example X.

FIG. 37 is the infrared spectrum for the peak indicated by referencenumeral "350" on the GLC profile of FIG. 35 for the compound having thestructure: ##STR47## prepared according to Example X.

FIG. 38 is the NMR spectrum for the peak indicated by reference numeral"351" on the GLC profile of FIG. 35 for the compound having thestructure: ##STR48## prepared according to Example X.

FIG. 39 is the infrared spectrum for the peak indicated by referencenumeral "351" on the GLC profile of FIG. 35 for the compound having thestructure: ##STR49## prepared according to Example X.

DETAILED DESCRIPTION OF THE DRAWINGS

Referring to FIG. 1A, the peak indicated by reference numeral 10 is thepeak for the compound having the structure: ##STR50##

Referring to FIG. 1B, the peak indicated by reference numeral 11 is thepeak for the compound having the structure: ##STR51##

Referring to FIG. 4, the peak indicated by reference numeral 42 is thepeak for the reaction product having the structure: ##STR52## The peakindicated by reference numeral 41 is the peak for the starting materialhaving the structure: ##STR53## The peak indicated by reference numeral43 is the peak for the reaction solvent, diethyl ether.

Referring to FIG. 7, the peak indicated by reference numeral 72 is thepeak for the reaction product having the structure: ##STR54## The peakindicated by reference numeral 71 is the peak for the starting materialhaving the structure: ##STR55## The peaks indicated by reference numeral73 are for the reaction solvent, diethyl ether.

Referring to FIG. 13, the peak indicated by reference numeral 130 is thepeak for the reaction product having the structure: ##STR56## The peakindicated by reference numeral 131 is the peak for the reaction solvent,tetrahydrofuran.

Referring to FIG. 16, the peak indicated by reference numeral 160 is thepeak for the reaction product of Example V having the structure:##STR57## The peak indicated by reference numeral 161 is for thestarting material having the structure: ##STR58## The peaks indicated byreference numeral 162 are for the reaction solvent, diethyl ether.

Referring to FIG. 19, the peak indicated by reference numeral 191 is thepeak for the compound having the structure: ##STR59## prepared accordingto Example VI. The peak indicated by reference numeral 190 is the peakfor the compound having the structure: ##STR60## The peak indicated byreference numeral 192 is the peak for reaction for the reaction solventand starting material, acetic anhydride.

Referring to FIG. 22, the peak indicated by reference numeral 220 is thepeak for the reaction product of Example VII(A), the compound having thestructure: ##STR61##

Referring to FIG. 29, the peak indicated by reference numeral 290 is thepeak for the reaction product of Example VIII, the compound having thestructure: ##STR62## The peak indicated by reference numeral 291 is thepeak for the starting material having the structure: ##STR63## The peaksindicated by reference numeral 292 are for the reaction solvent, diethylether.

Referring to FIG. 32, the peak indicated by reference numeral 320 is thepeak for the reaction product having the structure: ##STR64## The peakindicated by reference numeral 321 is the peak for the starting materialhaving the structure: ##STR65## The peaks indicated by reference numeral322 are for the reaction solvent, tetrahydrofuran.

Referring to FIG. 35, the peak indicated by reference numeral 350 is thepeak for the reaction product of Example X, the compound having thestructure: ##STR66## The peak indicated by reference numeral 351 is thepeak for the second reaction product of Example X, the compound havingthe structure: ##STR67## The peak indicated by reference numeral 352 isthe peak for the reaction solvent and starting material, aceticanhydride.

THE INVENTION

It has now been discovered that novel solid and liquid perfumecompositions, colognes and perfumed articles having intense, substantiveand long lasting patchouli, ambery, earthy, woody, peach, mimosa,camphoraceous, mahogany, piney, animalic and musky aromas withpatchouli, camphoraceous, earthy, musty, woody, green and fruitytopnotes may be provided by use of the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention defined according to thestructure: ##STR68## wherein R₃, R₄, R₅ and R₆ represent the same ordifferent hydrogen or methyl; wherein the dashed line line represents acarbon carbon single bond or a carbon carbon double bond; wherein thewavy line represents a carbon carbon single bond or a carbon carbondouble bond; with the proviso that when the wavy line is a carbon carbonsingle bond then the dashed line is a carbon carbon single bond; whereinY is a moiety selected from the group consisting of:

(i) the moiety having the structure: ##STR69## (ii) the moiety havingthe structure: ##STR70## (iii) the moiety having the structure:##STR71## wherein R₂ represents hydrogen, C₁ -C₄ lower alkyl or C₁ -C₂acyl; and wherein R₁ represents C₁ -C₄ lower alkyl with the additionalproviso that when Y is the moiety: ##STR72## then the dashed line is acarbon carbon single bond.

The 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention may be produced by first carrying out the well knownDiels-Alder reaction: ##STR73## described and exemplified in U.S. Pat.No. 3,911,018 issued on Oct. 7, 1975, the specification for which isincorporated by reference herein That reaction is also described in U.S.Pat. No. 2,933,506 issued in April of 1960, the specification for whichis incorporated by reference herein. In the foregoing reaction, R₃, R₄,R₅ and R₆ each represent the same or different methyl or hydrogen.

The resulting product having the structure: ##STR74## may then bereacted with an organometallic compound such as methyl lithium, methylmagnesium chloride or methyl magnesium bromide according to the genericreaction: ##STR75## which is exemplified by the reactions: ##STR76##(using methyl lithium) or: ##STR77## (using methyl magnesium bromide)or: ##STR78## (using methyl magnesium chloride). In the foregoingreaction: ##STR79## M, accordingly, represents lithium or magnesiumhalide such as magnesium bromide or magnesium chloride and R₁ representsmethyl or ethyl.

The resulting organometallic compound having the structure: ##STR80##may then be hydrolyzed in acetic media using, for example, aqueoushydrochloric acid or aqueous ammonium chloride according to thereaction: ##STR81## exemplified by the reaction: ##STR82##

The resulting product defined according to the structure: ##STR83## canbe used "as is" for its perfumery properties or may be further reactedas set forth, infra.

Alternatively, the compound having the structure: ##STR84## may behydrogenated using hydrogen and a catalyst such as palladium orpalladium on carbon or palladium on calcium carbonate according to thereaction: ##STR85## wherein the dashed line represents a carbon carbonsingle bond or a carbon carbon double bond and the wavy line representsa carbon carbon single bond or a carbon carbon double bond with theproviso that when the wavy line is a carbon carbon single bond then thedashed line is a carbon carbon single bond. The hydrogenation reactioncan be carried out to the extent wherein both carbon carbon double bondsare hydrogenated thusly: ##STR86## or can be carried out where a portionof the product contains carbon-carbon unsaturation per the structure:##STR87## according to the reaction: ##STR88## as exemplified in ExampleVII(B) and VII(C), infra.

The reaction products having the structures: ##STR89## are both novelcompounds.

The resulting products: ##STR90## may then be reacted with methyllithium or a methyl magnesium halide such as methyl magnesium bromide ormethyl magnesium chloride according to the reactions: ##STR91## oraccording to the generic reaction: ##STR92## wherein M represents Li,MgBr or MgCl and R₁ represents C₁ -C₄ lower alkyl.

In the alternative, the reaction also carried out is as follows:##STR93## when the precursor is only partially hydrogenated.

The resulting organometallic compounds may then be hydrolyzed in thepresence of an acid hydrolysis reagent such as hydrochloric acid orammonium chloride according to the reaction: ##STR94## or the reaction:##STR95## The resulting products having the structures: ##STR96## showngenerically as the structure: ##STR97## may then be used "as is" fortheir perfumery properties or they may be further reacted, for example,forming an alkyl ether, a methylene derivative (in the case where R₆ ishydrogen) or an ester such as a formate or acetate.

In forming the ether, the compounds defined according to the genericstructure: ##STR98## for example, the compound having the structure:##STR99## may be reacted with an alkali metal hydride such as sodiumhydride or potassium hydride having the formula:

    M'H

wherein M' is sodium or potassium according to the reaction: ##STR100##The resulting organometallic compound is then reacted with either anacyl halide, an acyl anhydride or an alkyl halide according to thereaction: ##STR101## wherein R₂ ' is hydrogen or methyl or according tothe reaction: ##STR102## wherein X' represents chloro, bromo or iodo andR₂ represents C₁ -C₂ acyl or C₁ -C₄ alkyl. Thus the compound:

    R.sub.2 X'

can be an acyl halide or an alkyl halide. Examples of acyl halides areacetyl chloride. Examples of alkyl halides are methyl iodide or methylchloride. More specifically, reactions, to wit: ##STR103## can takeplace; or in the case of acetic anhydride, the reaction can proceeddirectly from the tertiary alcohol thusly: ##STR104## However, in thecase of using acetic anhydride, the majority of the reaction product,rather than being the ester having the structure: ##STR105## or thestructure: ##STR106## or the structure: ##STR107## includes in majorproportion compounds having the structures: ##STR108## as well as thecompound having the structure: ##STR109## In carrying out the Grignardreactions: ##STR110## the Grignard reagent, methyl lithium or methylmagnesium chloride or methyl magnesium bromide or ethyl magnesiumchloride or ethyl magnesium bromide, is formed in solution usually in asolution of diethyl ether or tetrahydrofuran. While maintaining thereaction temperature at from -5° C. up to +5° C., the precursor ketonehaving the structure: ##STR111## is slowly added to the reaction massthereby forming the organometallic compound defined according to thestructure: ##STR112## The resulting organometallic compound having thestructure: ##STR113## is then hydrolyzed in aqueous acidic media, forexample, 10% acetic acid or 5% hydrochloric acid or 10% ammoniumchloride in water, at room temperature thereby forming the tertiaryalcohol defined according to the structure: ##STR114##

The resulting product is then fractionally distilled and used "as is" orfurther reacted.

In carrying out the hydrogenation (a reduction) reaction, that is thereaction, to wit: ##STR115## or the reaction: ##STR116## or thereaction: ##STR117## to form the compounds having the structure:##STR118## The reaction is carried out under high pressure. When desiredto form the product having the structure: ##STR119## the reaction iscarried out at 400-500 psig at a temperature of 75°-110° C. using apalladium on carbon catalyst with the percentage of palladium on carbonbeing between 1 and 2%. When it is desired to form a high proportion(e.g., 40-60%) of the compound having the structure: ##STR120## thenlower hydrogen pressures, e.g., 350 psig are used, using a lowertemperature, e.g., 35°-45° C.; and using the same catalyst, palladium orpalladium on carbon or palladium on calcium carbonate. In all cases, thereaction time is between about 3 hours and about 10 hours.

In carrying out the etherification reaction, one of the compoundsdefined according to the structure or a mixture of compounds definedaccording to the structure: ##STR121## is first reacted with an alkalimetal hydride defined according to the structure:

    M'H

according to the reaction: ##STR122## or the reaction: ##STR123## (forexample). Initially, the alkali metal hydride, e.g., sodium hydride, isadmixed with a suitable solvent, for example, tetrahydrofuran with theweight ratio of alkali metal hydride:solvent being from about 5% up toabout 15%, preferably 10%. At reflux conditions, e.g., from about 65° upto about 80° C. at between 1 and 1.5 atmospheres pressure, the alcoholhaving the structure: ##STR124## is added to the alkali metal hydridesolution over a period of about 2-4 hours, thereby forming theorganometallic salt defined according to the structure: ##STR125##

The compound defined according to the structure: ##STR126## is thenreacted with an alkyl halide such as methyl iodide defined according tothe formula:

    R.sub.2 X'

at a temperature of between about 20° up to about 40° C. in thetetrahydrofuran solution.

At the end of the reaction, the reaction mass is "worked up" by means ofquenching with water. The resulting product is fractionally distilled inorder to yield the substantially pure ether product defined according tothe structure: ##STR127## wherein R₂ " represents C₁ -C₄ lower alkyl.

In carrying out the esterification reaction (which forms a small amountof ester and a large amount of methylene-substituted compound definedaccording to the structure: ##STR128## with the ester defined accordingto the structure: ##STR129## wherein R₂ '" represents C₁ -C₂ acyl), thereaction is carried out with preferably a 50% excess amount of acylatingagent, e.g., acetic anhydride or acetyl chloride or formic acid, in thepresence of a catalyst such as methanesulfonic acid. When using themethanesulfonic acid catalyst or paratoluenesulfonic acid orparaxylenesulfonic acid, the reaction is carried out for a period oftime of between about 2 up to about 4 hours at a temperature of betweenabout 0° C. up to about 10° C. Thus, for example, the reaction that iscarried out is as follows: ##STR130## with a large proportion of thecompound having the structure: ##STR131## being prepared. The resultingproduct is then "worked up" as by quenching using water and aqueoussodium bicarbonate followed by drying of the resulting product andfractional distillation to yield the resulting mixture of compoundscontaining a major proportion of compounds defined according to thestructure: ##STR132##

The following Table I sets forth the structure of compounds producedaccording to our invention and their perfumery properties:

                  TABLE I                                                         ______________________________________                                        Structure of                                                                  1(4'-methylpentyl)-4-substituted                                              ethylcyclohexane derivative                                                                     Perfumery Properties                                        ______________________________________                                         ##STR133##       A patchouli, ambery, earthy, woody, peach, mimosa and                         camphoraceous aroma with patchouli, camphoraceous,                            earthy, musty and woody topnotes.                           The compound having the                                                                         A patchouli aroma.                                          structure:                                                                     ##STR134##                                                                   prepared according to Example                                                 II, bulked distillation                                                       fractions 5-9.                                                                The compound having the                                                                         A woody and mahogany aroma.                                 structure:                                                                     ##STR135##                                                                   prepared according to Example                                                 III, bulked distillation                                                      fractions 7 and 8.                                                            The compound having the                                                                         A woody and patchouli aroma                                 structure:        with green topnotes.                                         ##STR136##                                                                   prepared according to Example                                                 IV, bulked distillation                                                       fractions 8-11.                                                               The compound having the                                                                         A camphoraceous and piney                                   structure:        aroma.                                                       ##STR137##                                                                   prepared according to Example                                                 V, bulked distillation                                                        fractions 8-12.                                                               The compound having the                                                                         A woody aroma.                                              structure:                                                                     ##STR138##                                                                   prepared according to Example                                                 VI, bulked distillation                                                       fractions 8-13.                                                               The compound having the                                                                         A woody, patchouli, animalic                                structure:        and musky aroma.                                             ##STR139##                                                                   prepared according to Example                                                 VIII, bulked distillation                                                     fractions 13-24.                                                              The compound having the                                                                         A patchouli, ambery and woody                               structure:        aroma with fruity topnotes.                                  ##STR140##                                                                   prepared according to Example                                                 IX, bulked distillation                                                       fractions 9-17.                                                               ______________________________________                                    

The 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention defined according to the structure: ##STR141## wherein R₃, R₄,R₅ and R₆ each represents hydrogen or methyl; wherein the dashed linerepresents a carbon carbon single bond or a carbon carbon double bond;wherein the wavy line represents a carbon carbon single bond or a carboncarbon double bond; with the proviso that when the wavy line is a carboncarbon single bond then the dashed line is a carbon carbon single bond;wherein Y is a moiety selected from the group consisting of: ##STR142##wherein R₂ is hydrogen, C₁ -C₄ lower alkyl or C₁ -C₂ acyl; and whereinR₁ represents C₁ -C₄ lower alkyl with the additional proviso that when Yis the moiety: ##STR143## then the dashed line is a carbon carbon singlebond, are capable of augmenting, enhancing or imparting intense,substantive and long lasting patchouli, ambery, earthy, woody, peach,mimosa, camphoraceous, mahogany, piney, animalic and musky aromas withpatchouli, camphoraceous, earthy, musty, woody, green and fruitytopnotes; and at the same time are non-discoloring in perfumecompositions.

The 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention and one or more auxiliary perfume ingredients including, forexample, alcohols (other than the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention), ketones, nitriles,esters (other than the 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivatives of our invention), cyclic esters (lactones), ethers (otherthan the 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivativesof our invention), thioethers, thiols, carboxylic acids, hydrocarbons,natural essential oils and synthetic essential oils may be admixed sothat the combined odors of the individual components produce a pleasantand desired fragrance, particularly and preferably in the naturalcitrusy or musky area. Such perfume compositions usually contain (a) themain note or the "bouquet" or the foundation stone of the composition;(b) modifiers which round off and accompany the main notes; (c)fixatives which include odorous substances which lend a particular noteto the perfume throughtout all stages of evaporation and substanceswhich retard evaporation; and (d) topnotes which are usuallylow-boiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics; however, theoverall sensory effect of the perfume composition will be at least thesum total of the effect of each of the ingredients. Thus, the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention can be used to alter, modify, impart or enhance the aromacharacteristics of or to a perfume composition, for example, byutilizing or moderating the olfactory reactions contributed by anotheringredient in the composition.

The amount of one or more of the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention which will be effective inperfume compositions as well as in perfumed articles and colognesdepends on many factors including the other ingredients, their amountsand the effects which are desired. It has been has found that perfumecompositions containing as little as 0.01% of at least one of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention or even less (e.g., 0.005%) can be used to impart a verynatural, long lasting and substantive intense patchouli, ambery, earthy,woody, peach, mimosa, camphoraceous, mahogany, piney, animalic and muskyaroma with patchouli, camphoraceous, earthy, musty, woody, green andfruity topnotes to soaps, cosmetics and other products. The amountemployed can range up to 70% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

At least one of the 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivatives of our invention are useful (taken alone or taken togetherwith other ingredients in perfume compositions) as (an) olfactorycomponent(s) in detergents and soaps, space odorants and deodorants,perfumes, colognes, toilet waters, bath preparations such as lacquers,brilliantines, pomades and shampoos; cosmetic preparations such ascreams, deodorants, hand lotions and sun screens; powders such as talcs,dusting powders, face powders and perfumed article compositions ofmatter such as perfumed polypropylene, perfumed polyethylene andperfumed polyurethanes, particularly long lasting or partially shortlasting mixtures of, for example, encapsulated perfumes suspended infree perfume compositions and the like.

When used as an olfactory component, as little as 0.1% of at least oneof the 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives ofour invention will suffice to impart an intense, long lasting andsubstantive non-discoloring patchouli, ambery, earthy, woody, peach,mimosa, camphoraceous, mahogany, piney, animalic and musky aroma withpatchouli, camphoraceous, earthy, musty, woody, green and fruitytopnotes. Generally no more than 3% of at least one of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention based on the ultimate end product is required in the perfumecomposition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for at least one of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention. The vehicle can be a liquid such as a non-toxic alcohol(e.g., ethyl alcohol), a non-toxic glycol (e.g., propylene glycol or1,2-butylene glycol or sorbitol) or the like. The carrier can be anabsorbent solid such as a gum (e.g., gum arabic, xanthan gum, guar gumor the like) or components for encapsulating the material (such asgelatin or ethyl cellulose as by coacervation).

When used as a component of a perfumed article such as a perfumedplastic or solid or liquid anionic, cationic, nonionic or zwitterionicdetergent or a drier-added fabric softener article or fabric softenercomposition or a shampoo or a soap, the range of at least one of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention usable varies from 0.005% up to about 5% by weight of theperfumed article. The lower range of this range, e.g., 0.005% up to 0.1%of at least one of the 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivatives of our invention, is most prefered when using it in adrier-added fabric softener article or fabric softener composition inview of the need for a "non-perfumy" but pleasant head space aroma abovethe batch of clothes dried using the drier-added fabric softener articleor fabric softener composition in a standard automatically operatedtumble drier.

It will thus be apparent that at least one of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention can be utilized to augment, alter, modify or enhance sensoryproperties, particularly organoleptic properties of a wide variety ofconsumable materials.

The representation of the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention defined according to thestructure: ##STR144## are intended to include herein the each of thevarious stereoisomers thereof including, but not limited to thestereoisomers depicted as follows: ##STR145##

The following examples are illustrative and the invention is to beconsidered to be restricted thereto only as indicated in the appendedclaims. Example A sets forth a process for producing precursor ketonesof our invention. Examples I-X set forth processes for preparing the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention. Examples XI, et seq., set forth organoleptic utilities of the1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives of ourinvention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE A

Reaction: ##STR146##

3-Methyl-3-pentenone (2,060 grams, 95%) is added in 15 minutes to asuspension of aluminum chloride (90 grams) in toluene (2 kilograms). Theinitial exotherm dies out after approximately 5% of the3-methyl-3-pentenone is added. The mass is warmed to 35° C., and myrcene(3,530 grams, 77%) is added over a period of 2 hours with externalcooling as needed to maintain the reaction mixture at 35°-40° C. Themixture is stirred at 35°-40° C. for 2 hours, 27 grams aluminum chlorideis added, and the mass is stirred for an additional 9 hours at 35°-40°C.

After standing overnight at room temperature, the mixture is washed at40° C. with 10% sodium chloride solution and 15% sodium sulfatesolution. The washed organic solution is mixed with 100 gramstriethanolamine, 100 grams PRIMOL® (U.S.P. white mineral oil availablefrom Exxon Incorporated of Linden, N.J.) and 5 grams IONOL® (RegisteredTrademark of the Shell Chemical Company; butylated hydroxy toluene) andis distilled rapidly at 2.35 mm/Hg using a short column to give 3,999grams of product, boiling point 146°-150° C. at 2-3.5 mm/Hg.

EXAMPLE I PREPARATION OFα,α,1,6-TETRAMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOL

Reactions: ##STR147##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,cooling coil, heating mantle and addition funnel is placed 1,600 ml of a1.4 molar solution of methyl lithium in diethyl ether. The methyllithium solution is cooled to 0° C.

Over a period of 2 hours, 374 grams (1.6 moles) of the compound havingthe structure: ##STR148## is added to the methyl lithium solution, withstirring while maintaining the reaction temperature at 0° C. Thecompound having the structure: ##STR149## is thus formed.

The resulting mixture is then quenched with a 10% aqueous solution ofacetic acid (equal volume).

The resulting mixture is transferred to a separatory funnel and theorganic phase is separated from the aqueous phase. The organic phase isthen washed with three volumes of saturated aqueous sodium bicarbonatefollowed by 1 liter of water. The resulting product is then filteredthrough anhydrous magnesium sulfate in order to dry it. The resultingproduct (860 grams) is then distilled in a "rushover column" yieldingthe following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       37/49         61/110    80/5.0                                        2       117           150       1.13                                          3       151           165       1.48                                          4        90           195       2.43                                          ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled yielding the followingfractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       98/125    156/158     1.51/1.46                                                                            9:1                                      2       112       158         1.52   9:1                                      3       119       157         1.49   9:1                                      4       127       158         1.95   9:1                                      5       125       158         1.72   9;1                                      6       112       158         2.16   9:1                                      7       139       158         2.13   9:1                                      8       131       158         2.02   9:1                                      9       125       158         1.42   9:1                                      10      129       159         1.55   9:1                                      11      139       159         2.29   9:1                                      12      130       158         1.47   9:1                                      13      131       158         1.48   9:1                                      14      133       158         1.56   9:1                                      15      137       158         1.25   9:1                                      16      137       158         1.73   9:1                                      17      137       163         2.34   9:1                                      18      137       165         2.05   9:1                                      19      156       168         6.10   9:1                                      20      154       167         2.10   9:1                                      21      136       165         1.50   9:1                                      22      132       165         1.40   9:1                                      23      128       165         1.46   9:1                                      24      129       166         1.45   9:1                                      25      129       166         1.43   9:1                                      26      145       166         2.30   9:1                                      27      139       166         1.91   9:1                                      28      141       166         2.09   9:1                                      29      130       162         1.44   9:1                                      30      131       165         1.41   9:1                                      31      132       164         1.43   9:1                                      32      132       164         1.42   9:1                                      33      141       168         1.50   9:1                                      34      134       166         1.52   9:1                                      35      139       168         1.81   7:3                                      36      142       168         2.03   7:3                                      37      142       168         1.95   7:3                                      38      156       169         2.25   7:3                                      39      148       169         2.82   7:3                                      40      112       170         3.14   7:3                                      41      154       169         1.52   7:3                                      42      142       164         2.11   7:3                                      43      140       185         1.80   7:3                                      44      123       200         1.95   7:3                                      ______________________________________                                    

Distillation Fractions 22-27 are bulked for use for their organolepticproperties. Fractions 22-38 are bulked for use in subsequent reactions,e.g., Example IV, infra, and Example VI, infra.

EXAMPLE II PREPARATION OFα,α-DIMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOL

Reactions: ##STR150##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser, cooling coil, heating mantles and addition funnel isplaced 1,600 ml of a solution of 1.4 molar methyl lithium in diethylether (2.24 moles). The methyl lithium solution is cooled to 0° C. andover a period of 2 hours, 330 grams (1.6 moles) of the compound havingthe structure: ##STR151## is added to the reaction mass with stirringwhile maintaining the reaction temperature at 0° C. The product thusformed has the structure: ##STR152##

One liter of 10% aqueous acetic acid is then admixed with the resultingreaction product and the temperature of the reaction mass is allowed towarm up to room temperature, 25° C.

The reaction mass is then transferred to a 5 liter separatory funnel andthe organic phase is separated from the aqueous phase.

The organic phase is then washed with three 1 liter portions ofsaturated aqueous sodium bicarbonate solution followed by one 1 literportion of water. The resulting product is then filtered throughanhydrous sodium sulfate yielding 1,364 grams of crude product.

This material is then fractionally distilled on a "rushover" columnyielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       32/65         81/150    26.2/165                                      2       113           161       6.90                                          3       143           170       4.55                                          4       123           229       3.14                                          ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled yielding the followingfractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       77/114    133/138     1.35/1.45                                                                            9:1                                      2       112       139         1.34   9:1                                      3       119       141         1.29   9:1                                      4       119       140         1.26   9:1                                      5       124       143         1.26   9:1                                      6       125       145         1.13   9:1                                      7       126       145         1.16   9:1                                      8       129       146         1.52   9:1                                      9       122       144         1.12   9:1                                      10      121       161         1.14   9:1                                      11       92       201         1.13   9:1                                      ______________________________________                                    

Distillation fractions 5-9 are bulked for use in perfume compositions.

EXAMPLE III PREPARATION OFα,α,6,6-TETRAMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOL

Reactions: ##STR153##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser, cooling coil, heating mantle and addition funnel isplaced 1,600 ml of a 1.4 molar solution of methyl lithium in diethylether (2.24 moles). The methyl lithium solution is cooled to 0° C. andover a period of 2 hours, 371 grams (1.6 moles) of the compound havingthe structure: ##STR154## is added to the reaction mass, whilemaintaining the reaction mass at a temperature of 0° C.

The resulting product has the structure: ##STR155##

The resulting product is then quenched with 1 liter of 10% aqueousacetic acid. The temperature of the reaction mass is permitted to riseto room temperature (26° C.). The resulting product is transferred to aseparatory funnel and the organic phase is separated from the aqueousphase. The organic phase is washed with three 1 liter volumes ofsaturated sodium bicarbonate. The resulting product is then filteredthrough anhydrous sodium sulfate and distilled on a "rushover" columnyielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       29/58         43/180    12/70                                         2       130           165       6.90                                          3       165           210       4.30                                          ______________________________________                                    

Fraction 2 is redistilled yielding the following fractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       39/88     155/163     3.2/26.4                                                                             9:1                                      2       115       158         3.32   9:1                                      3       124       112         2.45   9:1                                      4       134       161         2.80   9:1                                      5       133       156         2.34   9:1                                      6       156       164         2.18   9:1                                      7       139       173         1.99   9:1                                      8       156       192         2.55   9:1                                      9       153       205         2.65   1:9                                      ______________________________________                                    

Distillation fractions 7 and 8 are bulked for their organoleptic uses.

EXAMPLE IV PREPARATION OF THE METHYL ETHER OFα,α,1,2-TETRAMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOL

Reactions: ##STR156##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser, heating mantle and addition funnel is placed 62.4grams of sodium hydride and 631 grams of tetrahydrofuran. The resultingsodium hydride solution is heated to reflux (64°-65° C.).

While refluxing the sodium hydride/tetrahydrofuran solution over aperiod of 3 hours, 500 grams (2 moles) of the compound having thestructure: ##STR157## is added to the reaction mass. At the end of the 3hour period, the compound present has the structure: ##STR158##

Over a period of 2 hours, 341 grams (2.4 moles) of methyl iodide isadded to the reaction mass with stirring while maintaining the reactionmass at a temperature of 69° C. At the end of the 2 hour period, thereaction mass is cooled to room temperature and washed with three 1liter volumes of water. The resulting product is then filtered throughanhydrous sodium sulfate.

The resulting product is then distilled on a "rushover" column to yieldthe following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       87            146       1.54                                          2       127           149       1.55                                          3       131           152       1.50                                          4       135           207       1.39                                          ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled yielding the followingfractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       49/130    148/158     0.966/1.09                                                                           9:1                                      2       128       156         0.936  9:1                                      3       134       157         1.13   9:1                                      4       131       152         1.09   9:1                                      5       133       157         1.03   9:1                                      6       128       157         0.528  4:1                                      7       125       159         0.954  4:1                                      8       128       159         1.01   4:1                                      9       134       159         0.948  4:1                                      10      130       161         0.936  4:1                                      11      131       164         0.960  4:1                                      12      135       176         0.890  3:2                                      13      135       193         0.890  1:9                                      14      137       200         0.995  1:9                                      ______________________________________                                    

Distillation fractions 8-11 consisting of the compound having thestructure: ##STR159## as confirmed by NMR, IR and mass spectral analysesare bulked for perfumery uses.

EXAMPLE V PREPARATION OFα-ETHYL-α,1,6-TRIMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOL

Reactions: ##STR160##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser, heating mantle and addition funnel is placed asolution of 1,600 ml of methyl lithium (1.4 molar) in diethyl ether(2.24 moles). The methyl lithium solution is cooled to 0° C. Over aperiod of 2 hours, 400 grams (1.6 moles) of the compound having thestructure: ##STR161## is added to the reaction mass, while maintainingthe reaction mass with stirring at a temperature of 0° C. The reactionmass is then stirred for an additional 2 hours at 0° C.

The reaction mass is then quenched with 1 liter of 10% aqueous aceticacid. The reaction mass is then transferred to a 5 liter separatoryfunnel and the aqueous phase is separated from the organic phase. Theorganic phase is washed with three 1 liter portions of saturated aqueoussodium bicarbonate solution followed by one 1 liter portion of water.The resulting product is then filtered through anhydrous sodium sulfateyielding 1,061 grams of crude product. The resulting product is thendistilled on a "rushover" column yielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       46            80/135    1.5/9.23                                      2       90            184       5.44                                          3       166           152       3.72                                          4       174           215       2.15                                          ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled on a fractionation columnyielding the following fractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       64/157    169/174     1.22/1.47                                                                            9:1                                      2       147       177         1.42   9:1                                      3       143       173         1.27   9:1                                      4       139       172         1.09   9:1                                      5       139       173         1.03   9:1                                      6       155       175         1.81   9:1                                      7       148       174         1.27   9:1                                      8       140       174         1.02   9:1                                      9       150       175         1.44   9:1                                      10      146       175         1.25   9:1                                      11      153       179         1.76   9:1                                      12      154       179         1.89   9:1                                      13      154       202         2.02   9:1                                      ______________________________________                                    

Distillation fractions 8-12 are bulked. Distillation fractions 8-12consist of the compound having the structure: ##STR162## as confirmed byNMR, IR and mass spectral analyses.

EXAMPLE VI PREPARATION OF MIXTURE OFα,α,1,6-TETRAMETHYL-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE-1-METHANOLACETIC ACID ESTER ANDα,α,1,6-TETRAMETHYL-1-(2-PROPENYL)-4-(4-METHYL-3-PENTENYL)-3-CYCLOHEXENE

Reaction: ##STR163##

Into a 3 liter reaction vessel equipped with stirrer, thermometer,addition funnel and cooling coils are placed 161 grams (1.58 moles) ofacetic anhydride and 2.92 grams of methanesulfonic acid. With stirring,the resulting mixture is cooled to -6° C. While maintaining the reactionmass at -6° C. over a period of 2 hours, 292 grams of the compoundhaving the structure: ##STR164## prepared according to Example I isadded to the reaction mass with stirring. At the end of the 2 hourperiod, the reaction mass is permitted to warm up to 2° C. andmaintained at 2° C. for a period of 4 hours.

The reaction mass is then quenched with 1 liter of water and added to aseparatory funnel. The organic phase is separated from the aqueous phaseand the organic phase is washed with two 1 liter volumes of 10% aqueoussodium bicarbonate followed by two 1 liter volumes of saturated aqueoussodium bicarbonate.

The resulting product is then filtered through anhydrous sodium sulfateyielding 240 grams of product. The resulting product is distilled on a"rushover" column yielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       32/35         52/161    1.93/76                                       2       42/45         62/153    2.35/25                                       3       126           181       0.880                                         4       130           145       2.05                                          5       143           200       1.75                                          ______________________________________                                    

Fractions 3 and 4 are bulked and redistilled on a fractionation columnyielding the following fractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       92/103    131/132     0.795/1.06                                                                           9:1                                      2       106       139         0.990  9:1                                      3       104       138         0.978  9:1                                      4       107       134         1.02   9:1                                      5       106       133         0.900  9:1                                      6       105       133         0.900  9:1                                      7       107       134         0.890  9:1                                      8       97        134         1.01   9:1                                      9       98        134         1.01   9:1                                      10      92        136         0.895  9:1                                      11      93        134         0.885  9:1                                      12      96        133         0.960  9:1                                      13      99        146         0.954  9:1                                      14      104       151         1.09   9:1                                      15      115       178         1.09   9:1                                      ______________________________________                                    

Distillation fractions 8-13 are bulked and contain 95 mole percent ofthe compound having the structure: ##STR165## and 5 mole percent of thecompound having the structure: ##STR166## as confirmed by NMR, IR andmass spectral analyses. Bulked distillation fractions 8-13 are used fortheir organoleptic properties.

EXAMPLE VII PREPARATION OFα,α,1,6-TETRAMETHYL-4-(4-METHYL-3-PENTENYL)-CYCLOHEXANE-1-METHANOLEXAMPLE VII(A)

Reaction: ##STR167##

Into a 2 liter autoclave equipped with hydrogen feedline is placed 1,281grams (5.47 moles) of the compound having the structure: ##STR168## and7 grams of a 1.5% palladium on carbon catalyst. The autoclave is sealedand heated to a temperature in the range of 75°-110° C. and pressurizedwith hydrogen to a pressure of 400 psig. The hydrogen pressure ismaintained at 400 psig for a period of 4 hours and the temperature ismaintained at 79°-110° C. for the 4 hour period.

At the end of the 4 hour period, the autoclave is cooled and opened andthe contents are filtered.

The resulting product is fractionally distilled yielding the followingfractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       51/31         71/84     140/6.2                                       2       123           151       1.56                                          3       121           151.9     1.39                                          4       129           152       1.99                                          5       114           152       0.655                                         6       110           153       0.570                                         7       140           198       0.520                                         ______________________________________                                    

Fractions 2-6 are bulked for subsequent use in Example VIII, infra. Theresulting product has the structure: ##STR169## as confirmed by NMR, IRand mass spectral analyses.

EXAMPLE VII(B)

Reactions: ##STR170##

Into a 2 liter autoclave equipped with hydrogen feedline are placed1,107 grams of the compound having the structure: ##STR171## and 6 gramsof a 1.5% palladium on carbon catalyst. The autoclave is sealed and thetemperature is raised to 39°-43° C. and pressurized with hydrogen at 350psig. The autoclave is maintained at a temperature of 39°-43° C. for aperiod of 6 hours and at a pressure of 350 psig. At the end of the 6hour period, the autoclave is cooled and opened and the contents arefiltered. The contents are fractionally distilled and the resultingproduct contains the following materials:

(i) 27% by weight of the compound having the structure: ##STR172## (ii)37% by weight of the compound having the structure: ##STR173## (iii) 29%by weight of the compound having the structure: ##STR174##

EXAMPLE VII(C)

Reactions: ##STR175##

Into a 2 liter autoclave equipped with hydrogen feedline are placed thefollowing materials:

(i) 1,074 grams of the compound having the structure: ##STR176## (ii) 5grams of a 1.5% palladium on carbon catalyst. The autoclave is sealedand the contents are heated to a temperature of 32° C. and pressurizedwith hydrogen at a pressure of 350 psig. The autoclave is maintained at32° C. and 350 psig for a period of 3 hours.

At the end of the 3 hour period, the autoclave is cooled and opened andthe contents are filtered. The resulting product contains the followingmaterials:

(i) 14% by weight of the compound having the structure: ##STR177## (ii)45% by weight of the compound having the structure: ##STR178## (iii) 30%by weight of the compound having the structure: ##STR179##

EXAMPLE VIII PREPARATION OFα,α,1,6-TETRAMETHYL-4-(4-METHYLPENTYL)-CYCLOHEXANE-1-METHANOL

Reactions: ##STR180##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,addition funnel, heating mantle and cooling coils is placed 1,600 ml ofa solution of methyl lithium in diethyl ether (1.4 molar; 2.24 moles).The methyl lithium solution is cooled to 0° C. With stirring over aperiod of 2 hours, 381 grams (1.6 moles) of the compound having thestructure: ##STR181##

prepared according to Example VII(A) is added to the reaction mass.

At the end of the 2 hour period, the reaction mass is stirred for 1.5hours at 0° C.

The reaction mass is then quenched with 1 liter of 10% aqueous aceticacid. The reaction mass is transferred to a 5 liter separatory funneland the organic phase is separated from the aqueous phase. The organicphase is washed with three 1 liter volumes of saturated sodiumbicarbonate followed by one 1 liter volume of water. The resultingproduct is then filtered through anhydrous sodium sulfate yielding 367grams of product. The resulting product is then fractionally distilledon a "rushover column" yielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       118           151       0.725                                         2       130           154       0.725                                         3       142           160       2.56                                          4       26            300       1.13                                          ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled yielding the followingfractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg.                                                                              Reflux                                    Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                            Ratio                                     ______________________________________                                        1       155       171         0.795 9:1                                       2       153       169         0.577 9:1                                       3       153       169         0.785 9:1                                       4       119       167         0.700 9:1                                       5       143       163         0.730 9:1                                       6       131       165         2.34  9:1                                       7       139       164         2.50  9:1                                       8       144       165.6       2.61  9:1                                       9       139       163.3       2.49  9:1                                       10      143       164.1       2.30  9:1                                       11      140       166.3       1.83  9:1                                       12      141       163.1       1.87  9:1                                       13      129       157         1.72  9:1                                       14      127       154         1.55  9:1                                       15      128       154         1.55  9:1                                       16      128       157         1.54  9:1                                       17      102       160         0.520 9:1                                       18      110       155         0.495 4:1                                       19      108       157         0.495 4:1                                       20      109       160         0.488 4:1                                       21      110       160         0.480 4:1                                       22      109       160         0.489 4:1                                       23      107       160         0.480 4:1                                       24      118       176         0.480 1:9                                       25      124       182         0.800 1:9                                       26      125       189         D.700 1:9                                       27      108       200         0.570 1:9                                       ______________________________________                                    

Fractions 13-25 are bulked for use in Example IX and for use for theirorganoleptic properties.

Bulked distillation fractions 13-25 consist of the compound having thestructure: ##STR182## as confirmed by NMR, IR and mass spectralanalyses.

EXAMPLE IX PREPARATION OF 1-(1-METHOXY-1-METHYL ETHYL)-1,2-DIMETHYL-4-(4-METHYLPENTYL)-CYCLOHEXANE

Reactions: ##STR183##

Into a 5 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and heating mantle are placed 62.4 grams of sodiumhydride and 624 ml tetrahydrofuran. The resulting sodium hydridesolution is heated to reflux at 65° C.

Over a period of 2 hours, 508 grams (2 moles) of the compound having thestructure: ##STR184## prepared according to Example VIII is added to thereaction mass. The reaction mass is then maintained at 82° C. for aperiod of 2 hours. The product in the reaction mass at this point intime has the structure: ##STR185##

The reaction mass is then cooled to room temperature and over a periodof 1.5 hours, 341 grams (2.4 moles) of methyl iodide is added to thereaction mass while maintaining the temperature of the reaction mass at22°-30° C.

The reaction mass is then maintained with stirring at 24°-30° C. for aperiod of 7 hours.

At the end of the 7 hour period, the reaction mass is quenched withthree 1 liter volumes of water. The reaction mass is then filteredthrough anhydrous sodium sulfate yielding 1,194 grams of product.

The reaction mass is then distilled on a "rushover column" yielding thefollowing fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            pressure                                      ______________________________________                                        1       33/57         50/113    87/143                                        2       124           156       0.924                                         3       137           200       0.890                                         ______________________________________                                    

Fractions 2 and 3 are bulked and redistilled on a fractionation columnyielding the following fractions:

    ______________________________________                                                Vapor     Liquid      Vacuum                                          Fraction                                                                              Temperature                                                                             Temperature mm/Hg. Reflux                                   Number  (°C.)                                                                            (°C.)                                                                              Pressure                                                                             Ratio                                    ______________________________________                                        1       112/140   154/158     1.36/13                                                                              9:1                                      2       139       156         1.34   9:1                                      3       139       156         1.32   9:1                                      4       141       156         1.32   9:1                                      5       142       157         1.56   9:1                                      6       143       157         1.57   9:1                                      7       143       157         1.32   9:1                                      8       144       158         1.27   9:1                                      9       143       158         1.27   9:1                                      10      144       157         1.28   9:1                                      11      147       160         1.28   9:1                                      12      130       158         1.28   9:1                                      13      130       160         1.27   9:1                                      14      130       157.2       1.26   9:1                                      15      131       158         1.29   9:1                                      16      130       160.1       1.26   9:1                                      17      132       157.3       1.30   9:1                                      18      132       162.2       1.30   9:1                                      19      133       157.7       1.33   9:1                                      20      133       163         1.34   9:1                                      ______________________________________                                    

Distillation fractions 9-17 are bulked and consist of the compoundhaving the structure: ##STR186## as confirmed by NMR, IR and massspectral analyses. Bulked distillation fractions 9-17 are usedsubsequently for their organoleptic properties.

EXAMPLE X PREPARATION OF MIXTURE OFα,α,1,2-TETRAMETHYL-4-(4-METHYLPENTYL)CYCLOHEXANE METHANOL ACETATE ANDα,α,1,2-TETRAMETHYL-1-(2-PROPENYL)-4-(4-METHYL)-CYCLOHEXANE

Reaction: ##STR187##

Into a 2 liter reaction vessel equipped with stirrer, thermometer,reflux condenser and cooling coils are placed 306 grams (3 moles) ofacetic anhydride and 5.08 grams of methanesulfonic acid. The resultingmixture is cooled to 0° C. with stirring.

With stirring over a period of 2 hours, 508 grams (2 moles) of thecompound having the structure: ##STR188## is added to the reaction mass.The Compound having the structure: is prepared according to ExampleVIII, bulked distillation fractions 13-24. The reaction mass is stirredat 0° C. for a period of 2.5 hours.

At the end of the 2.5 hour period, the reaction mass is quenched withone 1 liter portion of water followed by two 1 liter portions of 10%aqueous sodium bicarbonate followed by two 1 liter portions of aqueoussaturated sodium bicarbonate.

The resulting product is then filtered through anhydrous sodium sulfateand distilled on a "rushover" column yielding the following fractions:

    ______________________________________                                                Vapor         Liquid    Vacuum                                        Fraction                                                                              Temperature   Temperature                                                                             mm/Hg.                                        Number  (°C.)  (°C.)                                                                            Pressure                                      ______________________________________                                        1       98/113        131/120   0.37/0.4                                      2       99            200       0.557                                         ______________________________________                                    

Bulked distillation fractions 1 and 2 contain 82 mole percent of thecompound having the structure: ##STR189## and 18 mole percent of thecompound having the structure: ##STR190## as confirmed by NMR, IR andmass spectral analyses taken together with GLC analysis. The resultingmixture is used subsequently for its organoleptic properties.

EXAMPLE XI FRAGRANCE FORMULATIONS

To demonstrate the use of the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention prepared according toExamples I, II and III in magnolia, musk and citrusy formulations, thefollowing formulae are prepared:

    ______________________________________                                                           Parts by Weight                                            Ingredients          XI (A)  XI (B)  XI (C)                                   ______________________________________                                        Phenylethyl alcohol  200     25      25                                       Geraniol             400     25      25                                       Trichloromethylphenyl carbinyl acetate                                                             20      5       5                                        Phenylethyl acetate  60      5       5                                        Undecylenic aldehyde (10% in diethyl                                                               5       0       0                                        phthalate)                                                                    n-Nonyl aldehyde (10% in diethyl phthalate)                                                        2       0       0                                        Musk ketone          10      150     20                                       Musk ambrette        10      150     20                                       Eugenyl phenyl acetate                                                                             20      5       5                                        Citronellol          100     100     400                                      Vanillin (10% in diethyl phthalate)                                                                6       6       6                                        Eugenol              30      5       5                                        Citronellyl formate  30      5       5                                        Geranyl acetate      10      5       5                                        Linalool             40      20      20                                       Geranyl phenyl acetate                                                                             50      20      20                                       Cis-beta, Gamma-hexenyl acetate                                                                    2       0       0                                        1-(2,5,5-Trimethyl-1,3-cyclohexadien-                                                              5       5       5                                        1-yl)-1,3-butanedione                                                         Farnesene isomer mixture produced                                                                  60      60      40                                       according to Example I of U.S. Pat. No.                                       4,394,444 (the specification for which is                                     incorporated by reference herein).                                             ##STR191##          120     0       0                                        The compound having the structure:                                                                 0       120     0                                         ##STR192##                                                                   prepared according to Example II,                                             bulked distillation fractions 5-9                                             The compound having the structure:                                                                 0       0       120                                       ##STR193##                                                                   produced according to Example III,                                            bulked distillation fractions 7 and 8.                                        ______________________________________                                    

The addition of the compound having the structure: ##STR194## preparedaccording to Example I, bulked distillation fractions 22-27 adds to thefragrance of Example XI(A) patchouli, ambery, earthy, woody, peach,mimosa and camphoraceous undertones with patchouli, camphoraceous,earthy, musty and woody topnotes. Accordingly, the perfume compositionof Example XI(A) can be described as "a magnolia aroma with intensepatchouli, ambery, earthy, woody, peach, mimosa and camphoraceousundertones with patchouli, camphoraceous, earthy, musty and woodytopnotes".

The addition of the compound having the structure: ##STR195## preparedaccording to Example II, bulked distillation fractions 5-9 adds apatchouli undertone to this musk formulation. Accordingly, the perfumecomposition of Example XI(B) can be described as "a musk aroma withpatchouli undertones".

The addition of the compound having the structure: ##STR196## preparedaccording to Example III, bulked distillation fractions 7 and 8, adds awoody and mahogany undertone to this citrus formulation. Accordingly,the perfume composition of Example XI(C) can be described as "a citrusaroma with woody and mahogany undertones".

EXAMPLE XII FRAGRANCE FORMULATIONS

To demonstrate the use of the 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention prepared according toExamples IV, V and VI in magnolia, musk and citrusy formulations, thefollowing formulae are prepared:

    ______________________________________                                                           Parts by Weight                                            Ingredients          XII (A) XII (B) XII (C)                                  ______________________________________                                        Phenylethyl alcohol  200     25      25                                       Geraniol             400     25      25                                       Trichloromethylphenyl carbinyl acetate                                                             20      5       5                                        Phenylethyl acetate  60      5       5                                        Undecylenic aldehyde (10% in diethyl                                                               5       0       0                                        phthalate)                                                                    n-Nonyl aldehyde (10% in diethyl phthalate)                                                        2       0       0                                        Musk ketone          10      150     20                                       Musk ambrette        10      150     20                                       Eugenyl phenyl acetate                                                                             20      5       5                                        Citronellol          100     100     400                                      Vanillin (10% in diethyl phthalate)                                                                6       6       6                                        Eugenol              30      5       5                                        Citronellyl formate  30      5       5                                        Geranyl acetate      10      5       5                                        Linalool             40      20      20                                       Geranyl phenyl acetate                                                                             50      20      20                                       Cis-beta, Gamma-hexenyl acetate                                                                    2       0       0                                        1-(2,5,5-Trimethyl-1,3-cyclohexadien-                                                              5       5       5                                        1-yl)-1,3-butanedione                                                         Farnesene isomer mixture produced                                                                  60      60      40                                       according to Example I of U.S. Pat. No.                                       4,394,444 (the specification for which is                                     incorporated by reference herein).                                            The compound having the structure:                                                                 120     0       0                                         ##STR197##                                                                   prepared according to Example IV, bulked                                      distillation fractions 8-11.                                                  The compound having the structure:                                                                 0       120     0                                         ##STR198##                                                                   prepared according to Example V,                                              bulked distillation fractions 8-12.                                           The compound having the structure:                                                                 0       0       120                                       ##STR199##                                                                   produced according to Example VI,                                             bulked distillation fractions 8 and 13.                                       ______________________________________                                    

The addition of the compound having the structure: ##STR200## preparedaccording to Example IV, bulked distillation fractions 8-11 imparts tothe magnolia formulation of Example XII(A) woody and patchouliundertones with green topnotes. Accordingly, the perfume composition ofExample XII(A) can be described as "a magnolia aroma with intense woodyand patchouli undertones and green topnotes".

The addition of the compound having the structure: ##STR201## preparedaccording to Example V, bulked distillation fractions 8-12 adds to themusk formulation of Example XII(B) camphoraceous and piney undertones.Accordingly, the perfume composition of Example XII(B) can be describedas "a musk aroma with camphoraceous and piney undertones".

The addition of the compound having the structure: ##STR202## preparedaccording to Example VI, bulked distillation fractions 8-13, imparts tothe citrus formulation of Example XII(C) woody undertones. Accordingly,the perfume composition of Example XII(C) can be described as "a citrusaroma with woody undertones".

EXAMPLE XIII FRAGRANCE FORMULATIONS

To demonstrate the use of 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivatives of our invention prepared according toExamples VIII and IX in magnolia and musk formulations, the followingformulae are prepared:

    ______________________________________                                                               Parts by Weight                                        Ingredients              XIII (A)                                                                              XIII (B)                                     ______________________________________                                        Phenylethyl alcohol      200     25                                           Geraniol                 400     25                                           Trichloromethylphenyl carbinyl acetate                                                                 20      5                                            Phenylethyl acetate      60      5                                            Undecylenic aldehyde (10% in diethyl phthalate)                                                        5       0                                            n-Nonyl aldehyde (10% in diethyl phthalate)                                                            2       0                                            Musk ketone              10      150                                          Musk ambrette            10      150                                          Eugenyl phenyl acetate   20      5                                            Citronellol              100     100                                          Vanillin (10% in diethyl phthalate)                                                                    6       6                                            Eugenol                  30      5                                            Citronellyl formate      30      5                                            Geranyl acetate          10      5                                            Linalool                 40      20                                           Geranyl phenyl acetate   50      20                                           Cis-beta, Gamma-hexenyl acetate                                                                        2       0                                            1-(2,5,5-Trimethyl-1,3-cyclohexadien-                                                                  5       5                                            1-yl)-1,3-butanedione                                                         Franesene isomer mixture produced according to                                                         60      60                                           Example I of U.S. Pat. No. 4,394,444 (the                                     specification for which is incorporated by                                    reference herein).                                                            The compound having the structure:                                                                     120     0                                             ##STR203##                                                                   produced according to Example VIII,                                           bulked distillation fractions 13-24.                                          The compound having the structure:                                                                     0       120                                           ##STR204##                                                                   prepared according to Example IX,                                             bulked distillation fractions 9-17.                                           ______________________________________                                    

The addition of the compound having the structure: ##STR205## preparedaccording to Example VIII, bulked distillation fractions 13-24, impartsto the magnolia formulation of Example XIII(A) woody, patchouli,animalic and musk undertones. Accordingly, the perfume composition ofExample XIII(A) can be described as "a magnolia aroma with intensewoody, patchouli, animalic and musk undertones".

The addition of the compound having the structure: ##STR206## preparedaccording to Example IX, bulked distillation fractions 9-17 imparts tothe musk formulation of Example XIII(B) a patchouli, ambery and woodyundertone with fruity topnotes. Accordingly, the perfume composition ofExample XIII(B) can be described as "a musk aroma having patchouli,ambery and woody undertones with fruity topnotes".

EXAMPLE XIV PREPARATION OF SOAP COMPOSITION

100 Grams of soap chips are produced according to Example V of U.S. Pat.No. 4,058,487 issued on Nov. 15, 1977, the specification for which isincorporated by reference herein, as follows:

The sodium salt of an equal mixture of C₁₀ -C₁₄ alkane sulfonates (95%active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrousisopropanol and 125 pounds of dionized water at 150° F. In this mixtureis dissolved 10 pounds of partially hydrogenated coconut oil, fattyacids and 15 pounds of sodium mono-C₁₄ -alkylmaleate. The pH of thesolution is adjusted to 6.0 by the addition of a small amount of a 50%aqueous sodium hydroxide solution. The isopropanol is distilled off andthe remaining aqueous solution is drum dried. The resulting solidactives are then blended in a mixture with 10 pounds of water, 0.2pounds of titanium hydroxide and 0.75 pounds of one of the materials setforth below:

                  TABLE II                                                        ______________________________________                                        Perfume Ingredient                                                                              Aroma Profile                                               ______________________________________                                         ##STR207##       A patchouli, ambery, earthy, woody, peach, mimosa and                         camphoraceous aroma with patchouli, camphoraceous,                            earthy, musty and woody topnotes.                           The compound having the                                                                         A patchouli aroma.                                          structure:                                                                     ##STR208##                                                                   prepared according to Example                                                 II, bulked distillation                                                       fractions 5-9.                                                                The compound having the                                                                         A woody and mahogany aroma.                                 structure:                                                                     ##STR209##                                                                   prepared according to Example                                                 III, bulked distillation                                                      fractions 7 and 8.                                                            The compound having the                                                                         A woody, patchouli aroma with                               structure:        green topnotes.                                              ##STR210##                                                                   produced according to Example                                                 IV, bulked distillation                                                       fractions 8-11.                                                               The compound having the                                                                         A camphoraceous and piney                                   structure:        aroma.                                                       ##STR211##                                                                   produced according to Example                                                 V, bulked distillation                                                        fractions 8-12.                                                               The compound having the                                                                         A woody aroma.                                              structure:                                                                     ##STR212##                                                                   produced according to Example                                                 VI, bulked distillation                                                       fractions 8-13.                                                               The compound having the                                                                         A woody, patchouli, animalic                                structure:        and musky aroma.                                             ##STR213##                                                                   produced according to Example                                                 VIII, bulked distillation                                                     fractions 13-24.                                                              The compound having the                                                                         A patchouli, ambery and woody                               structure:        aroma with fruity topnotes.                                  ##STR214##                                                                   produced according to Example                                                 IX, bulked distillation                                                       fractions 9-17.                                                               Perfume composition of                                                                          A magnolia aroma with intense                               Example XI (A).   patchouli, ambery, earthy,                                                    woody, peach, mimosa and                                                      camphoraceous undertones with                                                 patchouli, camphoraceous,                                                     earthy, musty and woody                                                       topnotes.                                                   Perfume composition of                                                                          A musk aroma with patchouli                                 Example XI (B)    undertones.                                                 Perfume composition of                                                                          A citrus aroma with woody and                               Example XI (C).   mahogany undertones.                                        Perfume composition of                                                                          A magnolia aroma with intense                               Example XII (A).  woody and patchouli undertones                                                and green topnotes.                                         Perfume composition of                                                                          A musk aroma with                                           Example XII (B).  camphoraceous and piney                                                       undertones.                                                 Perfume composition of                                                                          A citrus aroma with woody                                   Example XII (C).  undertones.                                                 Perfume composition of                                                                          A magnolia aroma with intense                               Example XIII (A). woody, patchouli, animalic                                                    and musk undertones.                                        Perfume composition of                                                                          A musk aroma having                                         Example XIII (B). patchouli, ambery and woody                                                   undertones with fruity                                                        topnotes.                                                   ______________________________________                                    

The chips are then plodded into logs, cut to size and finally stampedinto bars, having a pH of approximately 6.9.

Each of the perfumed soaps of Table II above manifests an excellentcharacteristic aroma as indicated in Table II above. Furthermore, eachof the perfumed soaps is non-discoloring.

EXAMPLE XV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder prepared according to U.S.Pat. No. 4,058,472 and containing 5% by weight of the sodium salts of amixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface activecomponent, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkylcatechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35% ofsodium tetrapyrophosphate, 30% of sodium silicate, 20% of sodiumcarbonate, 3% of sodium carboxymethyl cellulose and 7% of starch ismixed with 0.15 grams of one of the perfume ingredients of Table II ofExample XIV, supra, until a substantially homogeneous composition isobtained. This composition has an excellent aroma as indicated accordingto Table II of Example XIV, supra.

EXAMPLE XVI PREPARATION OF COSMETIC POWDER COMPOSITIONS

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of one of the perfume materials of TableII of Example XIV, supra. Each of the cosmetic powders has an excellentaroma as set forth in Table II of Example XIV, supra.

EXAMPLE XVII PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents having aromas as set forth in Table II ofExample XIV, supra, are prepared by adding 0.10%, 0.15% and 0.20% ofeach of the perfume ingredients of Table II of Example XIV, supra. Theyare prepared by adding and homogeneously mixing the appropriate quantityof perfume material in the liquid detergent. The detergents all possessaromas as set forth in Table II of Example XIV, supra.

EXAMPLE XVIII PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUMES

Each of the compositions of Table II of Example XIV, supra, isincorporated into colognes at several concentrations, 2.0%, 2.5%, 3.0%,3.5%, 4.0% and 5.0% in 70%, 75%, 80%, 85% and 90% aqueous ethanol; andinto handkerchief perfumes at concentrations of 10%, 15%, 20% and 25%(in 80%, 85%, 90% and 95% aqueous ethanol). The use of each of theperfume ingredients as set forth in Table II of Example XIV, supra,affords distinctive aromas as set forth in Table II of Example XIV,supra.

EXAMPLE XIX PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Patent No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of a perfume material set forth in Table II of Example XIV, supra,until a substantially homogeneous composition is obtained in each case.Each of the compositions has an excellent aroma as set forth in Table IIof Example XIV, supra.

EXAMPLE XX

Utilizing the procedure of Example I of column 15 of U.S. Pat. No.3,632,396 (which is hereby incorporated by reference into the instantspecification), a nonwoven cloth substrate useful as a dryer-addedfabric-softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumingmaterial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀ -₂₂ HAPS;

22% isopropyl alcohol;

20% antistatic agent; and

2.5% of one of the perfume materials of Table II of Example XIV, supra.

A fabric-softening composition prepared as set forth above having anaroma characteristic as set forth in Table II of Example XIV, supra,consists of a substrate having a weight of about 3 grams per 100 squareinches, a substrate coating of about 1.85 grams per 100 square inches ofsubstrate and an outer coating of about 1.4 grams per 100 square inchesof substrate, thereby providing a total aromatized substrate and anouter coating weight ratio of about 1:1 by weight of the substrate. Theresulting aromas can be described as set forth in Table II of ExampleXIV, supra, and are imparted in pleasant manners to the head space inthe dryer on operation thereof using said dryer-added fabric-softeningnonwoven fabric.

EXAMPLE XXI PERFUMED POLYETHYLENE

Scented polyethylene pellets having a pronounced aroma as set forth inTable II of Example XIV, supra, are prepared as follows (in accordancewith Example III of U.S. Pat. No. 3,505,432 which is incorporated byreference herein):

75 Pounds of polyethylene having a melting point of about 220° F. areheated to about 230° F. in a container of the kind illustrated in FIGS.1 and 2 of U.S. Pat. No. 3,505,432. 25 Pounds of one of the perfumematerials of Table II of Example XIV, supra, are then quickly added tothe liquified polyethylene, the lid is put in place and the agitatingmeans are actuated. The temperature is maintained at about 225° F. andthe mixing is continued for about 15 minutes. The valve is then openedto allow flow of the molten polyethylene enriched with the perfumecontaining material to exit through the orifices as indicated in FIGS. 1and 2 of U.S. Pat. No. 3,505,432. The liquid falling through theorifices solidifies almost instantaneously upon impact with the movingcooled conveyor. Solid polyethylene beads or pellets having a pronouncedaroma as set forth in Table II of Example XIV, supra, are thus formed.Analysis demonstrates that the pellets contain about 25% of the perfumesubstance of Table II of Example XIV, supra, so that almost no losses inthe scenting substance occur. These pellets may be called masterpellets. 50 Pounds of the perfume substance containing master pelletsare then added to 1,000 pounds of unscented polyethylene powder and themass is heated to the liquid state. The liquid is molded into thinsheets or films. The thin sheets or films have a pronounced aroma as setforth in Table II of Example XIV, supra.

EXAMPLE XXII SCENTED POLYPROPYLENE

100 Pounds of polypropylene are heated to about 300° F. 30 Pounds of oneof the aroma materials of Table II of Example XIV, supra, are added tothe liquified polypropylene. The procedure is carried out in theapparatus of FIGS. 1 and 2 of U.S. Pat. No. 3,505,432. After mixing forabout 8 minutes, the valve is opened to allow the exit of thepolypropylene-scented material mixture whereby solid pellets having apronounced aroma as set forth in Table II of Example XIV, supra, areformed on the conveyor. The pellets thus obtained are then admixed withabout 20 times their weight of unscented polypropylene and the mixtureis heated and molded into flat discs. The flat discs have a strong andpleasant aroma as set forth in Table II of Example XIV, supra.

EXAMPLE XXIII

A perfumed polymer is produced by admixing a microporous polymerproduced according to one of Examples 194-236 of U.S. Pat. No. 4,247,498(the disclosure of which is incorporated by reference herein), andapplying a 0.5 mm/Hg. vacuum to the system. The resulting product isthen compressed into pellets and molded into fragrance-emitting plasticobjects, e.g., automobile dashboards.

What is claimed is:
 1. At least one 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivative defined according to the structure:##STR215## wherein R₃, R₄, R₅ and R₆ represent the same or differenthydrogen or methyl; wherein the dashed line represents a carbon carbonsingle bond or a carbon carbon double bond; wherein the wavy linerepresents a carbon carbon single bond or a carbon carbon double bond;with the proviso that when the wavy line is a carbon carbon single bondthen the dashed line is a carbon carbon single bond; wherein Yrepresents a moiety selected from the group consisting of: ##STR216##wherein R₂ is hydrogen, C₁ -C₄ lower alkyl or C₁ -C₂ acyl; and whereinR₁ is C₁ -C₄ lower alkyl with the additional proviso that when Y is themoiety: ##STR217## then the dashed line is a carbon carbon single bond.2. The 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative ofclaim 1 having the structure: ##STR218##
 3. The1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative of claim 1having the structure: ##STR219##
 4. The 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivative of claim 1 having the structure: ##STR220##5. The 1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative ofclaim 1 having the structure: ##STR221##
 6. A process for augmenting,enhancing or imparting an aroma in or to a consumable material selectedfrom the group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting, imparting or enhancing quantity and concentration ofat least one 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivative defined according to claim
 1. 7. A process for augmenting,enhancing or imparting an aroma in or to a consumable material selectedfrom the group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting, imparting or enhancing quantity and concentration ofat least one 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivative defined according to claim
 2. 8. A process for augmenting,enhancing or imparting an aroma in or to a consumable material selectedfrom the group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting, imparting or enhancing quantity and concentration ofat least one 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivative defined according to claim
 3. 9. A process for augmenting,enhancing or imparting an aroma in or to a consumable material selectedfrom the group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting, imparting or enhancing quantity and concentration ofat least one 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivative defined according to claim
 4. 10. A process for augmenting,enhancing or imparting an aroma in or to a consumable material selectedfrom the group consisting of perfume compositions, colognes and perfumedarticles comprising the step of adding to said consumable material anaroma augmenting, imparting or enhancing quantity and concentration ofat least one 1(4'-methylpentyl)-4-substituted ethylcyclohexanederivative defined according to claim
 5. 11. A perfume compositionconsisting essentially of a perfume base and intimately admixedtherewith in a perfume imparting, augmenting or enhancing quantity andconcentration, at least one 1(4'-methylpentyl)-4-substitutedethylcyclohexane derivative defined according to claim
 1. 12. A perfumecomposition consisting essentially of a perfume base and intimatelyadmixed therewith in a perfume imparting, augmenting or enhancingquantity and concentration, at least one1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative definedaccording to claim
 2. 13. A solid or liquid anionic, cationic, nonionicor zwitterionic detergent composition consisting essentially of a solidor liquid anionic, cationic, nonionic or zwitterionic detergent base andintimately admixed therewith an aroma augmenting, enhancing or impartingquantity or concentration of at least one1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives definedaccording to claim
 1. 14. A solid or liquid anionic, cationic, nonionicor zwitterionic detergent composition consisting essentially of a solidor liquid anionic, cationic, nonionic or zwitterionic detergent base andintimately admixed therewith an aroma augmenting, enhancing or impartingquantity or concentration of at least one1(4'-methylpentyl)-4-substituted ethylcyclohexane derivatives definedaccording to claim
 2. 15. A perfumed polymer consisting essentially of amicroporous polymer and containing in the interstices thereof an aromaimparting, augmenting or enhancing quantity of at least one1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative definedaccording to claim
 1. 16. A perfumed polymer consisting essentially of amicroporous polymer and containing in the interstices thereof an aromaimparting, augmenting or enhancing quantity of at least one1(4'-methylpentyl)-4-substituted ethylcyclohexane derivative definedaccording to claim
 2. 17. The organometallic compound having thestructure: ##STR222## wherein R₁ is C₁ -C₄ lower alkyl; R₃, R₄, R₅ andR₆ each represent the same or different hydrogen or methyl; the dashedline represents a carbon carbon single bond or a carbon carbon doublebond; the wavy line represents a carbon carbon single bond or a carboncarbon double bond with the proviso that when the wavy line is a carboncarbon single bond, then the dashed line is a carbon carbon single bond;and wherein M represents Li or MgX and wherein X is chloro or bromo. 18.The organometallic compound having the structure: ##STR223## wherein R₁represents C₁ -C₄ lower alkyl; R₃, R₄, R₅ and R₆ each represent the sameor different hydrogen or methyl; wherein the dashed line represents acarbon carbon single bond or a carbon carbon double bond; wherein thewavy line represents a carbon carbon single bond or a carbon carbondouble bond; with the proviso that when the wavy line is a carbon carbonsingle bond, then the dashed line is a carbon carbon single bond; andwherein M' is alkali metal.
 19. The ketone having the structure:##STR224## wherein the line: represents a carbon carbon single bond or acarbon carbon double bond and wherein R₃, R₄, R₅ and R₆ are the same ordifferent and each represents hydrogen or methyl.
 20. The ketone ofclaim 19 wherein the line: is a carbon carbon single bond.
 21. Theketone of claim 19 wherein the line: is a carbon carbon double bond. 22.A mixture of ketones defined according to claim 19 having the structures##STR225##